JP4455036B2 - Method for producing tertiary amine - Google Patents

Description

  The present invention provides a highly productive production method capable of obtaining a tertiary amine having an ester group useful as a surfactant, a surfactant intermediate, a pharmaceutical and agrochemical intermediate, etc., in high quality and in a high yield, The present invention relates to a quaternary ammonium salt composition obtained by quaternizing the tertiary amine, and a bleaching composition containing the quaternary ammonium salt and excellent in bleaching performance.

  In recent years, surfactants have various structures due to various requirements. Among them, the surfactant having an ester group is not only useful in terms of performance, but is also useful as a base considering the environment because it is easily decomposed immediately after use. Patent Document 1 describes a method of reacting an acid chloride and an alcohol as an esterification reaction. However, in order to promote the reaction, an alkali is necessary and it is necessary to remove a by-product salt. It is not suitable as an industrial production method.

On the other hand, Patent Document 2 describes heating at 140 to 230 ° C. using a fatty acid or a lower alkyl ester thereof and an alcohol as a known esterification reaction. However, when the boiling point of the raw alcohol is equal to or lower than the esterification reaction temperature, the raw alcohol is easily distilled out of the system together with water or lower alcohol desorbed during the reaction. For this reason, when the fatty acid or its lower alkyl ester and the alcohol are about equimolar, a mixture of the starting fatty acid or its lower alkyl ester and the desired ester compound can be obtained without completing the reaction. If a large amount of unreacted raw fatty acid or its lower alkyl ester is present, it leads to an increase in impurities and may cause quality problems due to the odor derived from the raw material. Even if distillation purification is performed for the purpose of removing the raw material from this mixture, if the difference in boiling points is small, the purification load becomes large in order to obtain a high-purity product, and it is difficult to produce it at low cost industrially. Even if the reaction is carried out with an excessive amount of alcohol, when the reaction is carried out at a temperature equal to or higher than the boiling point of the alcohol, it is difficult to complete the reaction by distilling the alcohol out of the system.
JP 2002-341593 A JP-A-8-245831

  The present inventors have found that when quaternary ammonium salts are used for bleaching agents, the presence of fatty acid lower alkyl esters (fatty acid methyl, fatty acid ethyl, etc.) degrades performance. It was also found that when a fatty acid is present during the production of a quaternary ammonium salt, it reacts with a dialkyl sulfuric acid to become a fatty acid lower alkyl ester. That is, these are not only quality problems due to odor, but also quaternary ammonium salts and bleaching agents obtained from the presence of a large amount of raw fatty acids or their lower alkyl esters when producing tertiary amines having ester groups. Means that performance cannot be fully demonstrated.

  Accordingly, an object of the present invention is to provide a highly productive and economically industrially valuable production method capable of obtaining a tertiary amine having an ester group with high purity and high yield. Another object of the present invention is to provide a quaternary ammonium salt composition obtained by quaternizing the tertiary amine, and a bleach composition containing the same and having excellent bleaching performance.

  The present invention relates to a general formula (1)

(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ³ represents a linear or branched alkylene group having 2 to 3 carbon atoms.)
An aminoalcohol having a boiling point of 200 ° C. or less (hereinafter referred to as aminoalcohol (1)), and a general formula (2)
R ⁴ COOR ⁵ (2)
(In the formula, R ⁴ represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, and R ⁵ represents H or an alkyl group having 1 to 3 carbon atoms.)
And a lower alkyl ester thereof (hereinafter referred to as “fatty acid etc. (2)”) is reacted with general formula (3)

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings.)
A method for producing a tertiary amine (3), wherein the amino alcohol (1) is dividedly charged when producing a tertiary amine having an ester group represented by (hereinafter referred to as a tertiary amine (3)). Provided are a quaternary ammonium salt composition obtained by quaternizing a tertiary amine (3) produced by the method with a dialkyl sulfuric acid, and a bleaching composition containing the quaternary ammonium salt composition. To do.

  According to the present invention, unreacted raw materials are efficiently reduced. As a result, tertiary amines having an ester group having no odor derived from raw materials can be obtained with high quality and high yield. A quaternary ammonium salt composition and a bleaching composition excellent in bleaching performance can be obtained.

[Method for producing tertiary amine]
The amino alcohol (1) having a boiling point of 200 ° C. or less used for the production of the tertiary amine (3) includes dimethylaminoethanol, dimethylamino-1-propanol, dimethylamino-2-propanol, diethylaminoethanol, 3-diethylamino. Examples include -1-propanol, 1-diethylamino-2-propanol, and 2- (diisopropanolamino) ethanol. Among these, dimethylaminoethanol, dimethylamino-1-propanol, and dimethylamino-2-propanol are preferable, and dimethylaminoethanol in which R ¹ and R ² are methyl groups and R ³ is an ethylene group is more preferable.

  Fatty acid etc. (2) is selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, coconut fatty acid, beef tallow fatty acid, hardened tallow fatty acid, etc. 1 type, or 2 or more types of mixed fatty acid, or those lower alkyl esters, such as methyl ester, ethyl ester, and isopropyl ester. Among these, fatty acids having 10 to 18 carbon atoms or methyl esters and ethyl esters thereof are preferable, and capric acid, lauric acid, myristic acid, and coconut fatty acid are more preferable.

  Examples of the tertiary amine (3) include the following compounds.

  In the method of the present invention, when the amino alcohol (1) is reacted with the fatty acid or the like (2), the amino alcohol (1) is dividedly charged. Examples of the split charging method include a method of dropping amino alcohol (1), a method of intermittent split charging of amino alcohol (1) in a plurality of times, a method of combining these methods, and the like. Among them, the method of dropping amino alcohol (1) is preferable, and the dropping speed in that case may be constant or unspecified, and may be changed to follow the reaction rate, for example.

  In the method of the present invention, in particular, at the initial stage of the esterification reaction, the molar ratio of amino alcohol (1) to fatty acid or the like (2) is in the range of (1) / (2) = 0.5 to 1.0. It is preferable. When this molar ratio is 0.5 or more, the amount of fatty acid or the like (2) is more suitable than aminoalcohol (1) at the reaction temperature, and side reactions other than the alcohol site are less likely to occur. When it is 0 or less, it is preferable because the amino alcohol (1) is difficult to distill off at an early stage even when the temperature reaches the boiling point of the amino alcohol (1) or higher. It is preferable to suppress the amount of amino alcohol (1) charged after the reaction starts. However, care must be taken because the reaction is difficult to complete if the amount charged is small. If the time during which the amino alcohol (1) is dividedly charged is long, it is preferable that distillation is suppressed before being used in the esterification reaction. Moreover, when it is long, amino alcohol (1) may be used efficiently. The time for split charging is preferably 1 to 10 hours, and more preferably 2 to 8 hours.

  The total amount of each of the amino alcohol (1) and the fatty acid (2) in the esterification reaction of the present invention is the molar ratio of the amino alcohol (1) and the fatty acid (2) (1) / (2) = 0.5-5.0 are preferable, 0.8-3.0 are more preferable, and 0.9-2.0 are particularly preferable.

  The temperature of the esterification reaction is preferably 50 to 250 ° C, more preferably 100 to 220 ° C, and particularly preferably 120 to 210 ° C.

  A catalyst may or may not be used during the esterification reaction. Examples of the catalyst to be used include tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, sodium methylate, sodium ethylate and the like.

  After the esterification reaction, the excess amino alcohol (1) has a boiling point of 200 ° C. or less and can be easily separated from the target ester compound with a large boiling point difference.

[Quaternary ammonium salt composition]
The quaternary ammonium salt composition of the present invention is obtained by quaternizing the tertiary amine (3) produced by the above production method with dialkyl sulfuric acid. Examples of the dialkyl sulfuric acid include dimethyl sulfuric acid and diethyl sulfuric acid.

  The molar ratio of the dialkyl sulfuric acid to the tertiary amine (3) is preferably dialkyl sulfuric acid / tertiary amine (3) = 0.9 / 1.0 to 1.2 / 1.0, 0.93 / 1. 0 to 1.1 / 1.0 is more preferable, and 0.95 / 1.0 to 1.0 / 1.0 is particularly preferable.

  Examples of the quaternization reaction solvent include alcohol solvents such as ethanol, propanol, and isopropanol.

  In the quaternization reaction of the present invention, the reaction temperature is not particularly limited, but is preferably 30 to 100 ° C, more preferably 40 to 90 ° C. The raw material is preferably charged by mixing a tertiary amine (3) and a solvent and adding dialkyl sulfuric acid dropwise at a set temperature. In this case, the dropping time of the dialkyl sulfuric acid is arbitrary, but since it generates heat, it is preferable to add the dropping so as not to exceed the reaction temperature. After completion of the quaternization reaction, it is poured into water to decompose unreacted dialkyl sulfuric acid to obtain the intended quaternary ammonium salt composition.

  The quaternary ammonium salt composition of the present invention contains a quaternary ammonium salt represented by the general formula (4) (hereinafter referred to as quaternary ammonium salt (4)) and water, and further contains a reaction solvent and the like. You may contain.

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent the above meanings, R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and Y ⁻ represents an alkyl sulfate ion.)
The content of the quaternary ammonium salt (4) in the quaternary ammonium salt composition of the present invention is preferably 0.1 to 35% by weight, more preferably 1.0 to 35% by weight. The content of water is preferably 30 to 99.8% by weight, and more preferably 30 to 98% by weight.

[Bleaching composition]
The bleaching composition of the present invention contains the quaternary ammonium salt composition of the present invention, hydrogen peroxide, a surfactant, a bleaching activator, etc., and the balance is water.

  As the surfactant to be blended in the bleaching composition of the present invention, a nonionic surfactant is preferable, and a nonionic surfactant represented by the general formula (5) is more preferable.

(Wherein R ⁷ is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or an aryl group optionally substituted by a linear or branched alkyl group having 1 to 18 carbon atoms, A represents a linear or branched alkylene group having 2 to 3 carbon atoms, Z represents H or an alkyl group having 1 to 3 carbon atoms, m represents an average value of 2 to 50, and m A may be the same May be different.)
In the general formula (5), R ⁷ is preferably an alkyl group or alkenyl group having 6 to 22 carbon atoms, and more preferably an alkyl group having 12 to 18 carbon atoms. A is preferably an ethylene group. m is a number of 2 to 50 indicating the average number of added moles of the oxyalkylene group, and 4 to 30 is preferable. Z is preferably H or a methyl group.

  Examples of the nonionic surfactant represented by the general formula (5) include the following compounds.

  Examples of the bleach activator to be blended in the bleach composition of the present invention include compounds represented by the general formula (6).

(In the formula, R ⁸ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms, and W represents —SO ₃ M or —COOM. M represents an organic or inorganic cation.)
Specific examples of the bleach activator include the following compounds.

  The content of each component in the bleaching composition of the present invention is preferably in the following range from the viewpoint of obtaining excellent bleaching performance and storage stability and obtaining an appropriate viscosity.

  The content of the quaternary ammonium salt composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, as the quaternary ammonium salt (4). The content of the surfactant is preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight, and particularly preferably 1 to 10% by weight. The content of hydrogen peroxide is preferably 0.5 to 10% by weight, more preferably 1 to 10% by weight, and particularly preferably 1 to 6% by weight. The content of the bleach activator is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, and particularly preferably 0.1 to 3% by weight.

  The bleaching composition of the present invention is basically a solution in which the above components are dissolved or dispersed in water, but it can improve the stability and freeze-restoration of the liquid at low temperatures, or can perform liquid separation at high temperatures. A hydrotrope may be added to prevent this. As such a hydrotrope, generally, a short chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin, etc. Examples include alcohols and polyhydric alcohols. The hydrotrope can be added in an amount of about 0 to 30% by weight in the bleaching composition.

  Moreover, you may mix | blend a metal sequestering agent with the bleaching composition of this invention. Specific examples of the metal sequestering agent include the following compounds.

(i) Phosphate compounds such as phytic acid or alkali metal salts or alkanolamine salts thereof
(ii) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid Phosphonic acids such as ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, or alkali metal salts or alkanolamine salts thereof
(iii) Phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, or alkali metal salts or alkanolamine salts thereof
(iv) amino acids such as aspartic acid, glutamic acid and glycine, or alkali metal salts or alkanolamine salts thereof
(v) aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, diencoric acid or alkali metal salts thereof Alkanolamine salt
(vi) organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, or these Alkali metal salt or alkanolamine salt
(vii) Alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A
(viii) Aminopoly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof, or polyethylenepolyamine poly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof.

  Among these, at least one selected from the group consisting of (ii), (v), (vi) and (vii) is preferable, and at least one selected from the group consisting of (ii) is more preferable. Such a sequestering agent is blended in the bleaching composition of the present invention in an amount of 0.0005 to 5% by weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 1% by weight.

  Further, the bleaching composition of the present invention can further contain various compounds. For example, phosphoric acid, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids typified by oxyquinoline and phenacetin, and DL-α-tocopherol, gallic acid derivatives, which are known as hydrogen peroxide stabilizers, Butylated hydroxyanisole (BHA), 2,6-di-tert-butyl-4-methylphenol (BHT) and the like can be added. The amount of these stabilizers to be added depends on the concentration of hydrogen peroxide, but is usually about 0 to 5% by weight, preferably 0.01 to 3% by weight.

  Furthermore, the bleaching composition of the present invention can contain substances known as anti-fading agents. Such substances include amino acids and amino acid salts such as phenylalanine, histidine, lysine, tyrosine and methionine, amino or imide compounds such as hydroxyiminodiacetic acid, and acrylonitrile and acrylonitrile having a quaternary ammonium group. And a copolymer with one or more kinds of polymerizable monomers. Although amino acids have optical isomers, optical isomers are not involved in the effects of the present invention. It is therefore possible to use chemically synthesized amino acids.

  In addition, Tinopal CBS (manufactured by Ciba-Geigy), Chinopearl SWN (manufactured by Ciba-Geigy) and color index fluorescence are used as fluorescent brighteners to increase the bleaching effect on white fiber. You may add 0-5 weight% of fluorescent whitening agents, such as whitening agent 28,40,61,71.

  Furthermore, 0 to 20% by weight of a thickener can be added for the purpose of increasing the viscosity of the composition and improving usability. In general, polyacrylates, maleic acrylate copolymers, carboxymethylcellulose derivatives, synthetic polymers such as methylcellulose and hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum, and kelzan, water-swellable clay minerals such as montmorillonite and vegam Etc. It is also possible to give viscoelastic rheological properties by combining an amphoteric surfactant and an anionic surfactant as described in JP-A-1-319600.

  Further, the bleaching composition of the present invention further contains appropriate amounts of various trace additives such as coloring agents such as dyes and pigments, fragrances, silicones, bactericides, ultraviolet absorbers, inorganic electrolytes (each from 0 to about About 2% by weight). The dye is particularly preferably an acid dye having hydrogen peroxide resistance in an acid solution.

  In the bleaching composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be blended as necessary in order to improve the bleaching performance.

  The pH of the bleaching composition of the present invention is 6 or less, preferably 3.5 or less. In order to adjust the pH, an inorganic acid such as sulfuric acid or phosphoric acid, an organic acid such as toluenesulfonic acid or benzenesulfonic acid, or the above-mentioned chelating agent or anionic surfactant can be used in an acid form. It is preferable to add or adjust using a caustic alkali such as sodium hydroxide or potassium hydroxide as necessary.

Further, the bleaching composition of the present invention is at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid, and alkali metal salts and alkaline earth metal salts thereof (for example, NaCl, Na ₂ SO ₄ , H ₃ PO ₄ etc.) may be contained in an amount of 0 to 5% by weight.

Production Example 1
200 g (1 mol) of lauric acid and 45 g (0.5 mol) of dimethylaminoethanol were charged into a 1 L four-necked flask and heated to 180 ° C. while stirring. After heating, the mixture was stirred for 1 hour, and 133 g (1.5 mol) of dimethylaminoethanol was added dropwise over 5 hours. After dropping, the mixture was stirred for 6 hours, and then cooled to 120 ° C., the system was made 1 kPa, and excess dimethylaminoethanol was recovered to obtain dimethylaminoethyl laurate.

Production Example 2
A lauric acid dimethylaminoethyl ester was obtained in the same manner as in Example 1 except that 62 g (0.7 mol) of dimethylaminoethanol was initially charged and 116 g (1.3 mol) was added dropwise.

Production Example 3
A coconut fatty acid dimethylaminoethyl ester was obtained in the same manner as in Production Example 1 except that 167 g (1 mol) of coconut fatty acid was used in place of lauric acid in Production Example 1.

Production Example 4
The same procedure as in Production Example 1 was performed except that dimethylamino-1-propanol was used in place of dimethylaminoethanol in Production Example 1 and the initial charge was 52 g and the drop charge was 154 g. Got.

Production Example 5
The same procedure as in Production Example 1 was conducted except that 214 g (1 mol) of methyl laurate was used in place of lauric acid in Production Example 1 and 5.4 g of sodium methylate was used as an esterification catalyst. An ester was obtained.

Comparative production example 1
The initial charge of dimethylaminoethanol was 89 g, and the reaction was carried out in the same manner as in Production Example 1 except that dimethylaminoethanol was not added dropwise during the reaction to obtain dimethylaminoethyl laurate.

Comparative production example 2
The initial charge of dimethylaminoethanol was 178 g, and the reaction was carried out in the same manner as in Production Example 1 except that dimethylaminoethanol was not added dropwise during the reaction to obtain dimethylaminoethyl laurate.

Table 1 shows the reaction rates of Production Examples 1 to 5 and Comparative Production Examples 1 and 2 and the evaluation results of the odor derived from the starting fatty acid. In addition, the reaction rate was calculated | required from the reduction | decrease amount of the acid value of raw material fatty acid. The odor was evaluated according to the following criteria for a tertiary amine having an ester group obtained by one panelist.
○: No odor derived from raw fatty acid is observed ×: odor derived from raw fatty acid is recognized

Examples 1-5, Comparative Examples 1-2
100 parts by weight of a tertiary amine having an ester group obtained in Production Examples 1 to 5 and Comparative Production Examples 1 and 2 and 40 parts by weight of ethanol were charged into a four-necked flask, heated to 60 ° C., and then a tertiary amine. And equimolar diethylsulfate was added dropwise. In order to raise temperature by reaction, it was dripped in the range of 60-70 degreeC, and ageing | curing | ripening was performed after completion | finish of dripping. After aging, it was diluted with water to obtain a quaternary ammonium salt composition comprising a 30% aqueous solution of a quaternary ammonium salt.

  The quaternary ammonium salt composition thus obtained was 0.5% by weight as an effective component of the quaternary ammonium salt, 2% by weight of hydrogen peroxide, 0.5% by weight of sodium dodecanoyloxy-p-benzenesulfonate, Dissolve 5% by weight of oxyethylene lauryl ether (5% adduct of ethylene oxide on average) in water and adjust the pH at 20 ° C. to 2.5 with 1/10 N aqueous sulfuric acid and / or 1/10 N aqueous sodium hydroxide. And a bleaching composition was obtained.

  About the obtained bleaching agent composition, the peracid production rate was measured by the following method. The results are shown in Table 2.

<Measurement of peracid production rate>
Add 20 mL of the bleaching composition to a commercially available powder detergent manufactured by Kao Corporation, 6.67 g of attack dissolved in 1 liter of tap water, and after 30 minutes, take 400 mL of this aqueous solution in a beaker and add 4 mL of 1% catalase aqueous solution. After stirring for 3 minutes, 10 mL of 20% sulfuric acid and 10 mL of 10% aqueous potassium iodide solution are added to develop a yellow color. Titration was carried out with 1/50 N sodium thiosulfate until the yellow color disappeared, and the peracid production rate was determined by the following equation.

Peracid production amount (mol) = (1/50) × (amount of sodium thiosulfate required for titration (L)) / 2
Peracid production rate (%) = [Peracid production amount (mol) / Amount of dodecanoyloxy-sodium p-benzenesulfonate (mol)] × 100
Reference example 1
About 100 parts by weight of a quaternary ammonium salt composition obtained by quaternizing the dimethylaminoethyl laurate obtained in Production Example 1 in the same manner as in Example 1, and adding 2 parts by weight of ethyl laurate, A bleach composition was produced in the same manner as in Example 1, and the peracid production rate was determined in the same manner. The results are shown in Table 2.

Claims (2)

General formula (1)

(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and R ³ represents a linear or branched alkylene group having 2 to 3 carbon atoms.)
An amino alcohol having a boiling point of 200 ° C. or less represented by the general formula (2)
R ⁴ COOR ⁵ (2)
(In the formula, R ⁴ represents a linear or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, and R ⁵ represents H. )
In a fatty acid represented, amino alcohol / fatty acid feed ratio of the initial reaction (molar ratio) was 0.5 to 1.0 and an amino alcohol / fatty acid charge ratio of total (molar ratio) is 0.8 to 5 The amino alcohol represented by the general formula (1) is made to react by splitting so as to be 0.0, and the general formula (3)

(In the formula, R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings.)
In manufactures tertiary amine having an ester group represented, then obtained the said tertiary amine is quaternized dialkyl sulfates, Formula (4)

(In the formula, R ¹ , R ² , R ³ and R ⁴ represent the above meanings, R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and Y ⁻ represents an alkyl sulfate ion.)
A bleaching composition comprising a quaternary ammonium salt represented by the formula: The bleaching composition according to claim ^1, wherein R ¹ and R ² in the general formula (1) are methyl groups and R ³ is an ethylene group.